3-(1H-Tetra­zol-5-yl)benzoic acid

Cheng, L.; Zhang, Y.-W.; Wang, J.-Q.; Zhang, G.

doi:10.1107/S1600536808041482

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o89

doi:10.1107/S1600536808041482

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3-(1H-Tetrazol-5-yl)benzoic acid

Lin Cheng,^a ^* Ya-Wen Zhang,^a Jian-Quan Wang ^a and Gong Zhang ^b

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 211189, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 8 December 2008; accepted 8 December 2008; online 10 December 2008)

The title compound, C₈H₆N₄O₂, is a difunctional compound with a carboxylate and a tetrazole residue. In the crystal structure, molecules are linked into two-dimensional sheets by intermolecular N—H⋯O and O—H⋯N hydrogen bonds.

Related literature

For the applications of tetrazoles, see: Chen & Tong (2007 ); Demko & Sharpless (2001 ). For related structures, see: Rizk et al. (2005 ).

Experimental

Crystal data

C₈H₆N₄O₂
M_r = 190.17
Monoclinic, P 2₁ /c
a = 5.2501 (10) Å
b = 16.805 (3) Å
c = 9.3290 (18) Å
β = 99.188 (3)°
V = 812.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 (2) K
0.45 × 0.14 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan SADABS (Sheldrick, 2000 ) T_min = 0.949, T_max = 0.985
5991 measured reflections
1583 independent reflections
1425 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.106
S = 1.07
1583 reflections
136 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯N4ⁱ	0.93 (2)	1.76 (2)	2.6664 (15)	164 (2)
N1—H1A⋯O1ⁱⁱ	0.94 (2)	1.77 (2)	2.7118 (16)	179.1 (19)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041482/bt2829sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041482/bt2829Isup2.hkl

checkCIF report

Comment top

Tetrazoles have been extensively investigated in organic synthetic chemistry for several decades due to the fact that they have wide ranging applications in pharmaceuticals, especially explosives, photography, information recording systems, agriculture, and as precursors to a variety of heterocycles (Chen et al. 2007; Demko et al. 2001). They have also been used as a type of important multidentate ligands in coordination chemistry. Here, we report the crystal structure of a new tetrazole, 3-(1H-tetrazol-5-yl)benzoic acid.

The title compound, C₈H₆N₄O₂, is a difunctional compound with carboxylate and tetrazole groups. The C=O distance of the carboxylate is 1.216 (2) Å, which is much shorter than the C—O distance of 1.311 (2) Å. In the tetrazole group, the N=N distance is 1.288 (2) Å, and the N—N distances are 1.343 (2) and 1.358 (2) Å, respectively. The C—N distance is 1.333 (2) Å, being close to the C=N distance of 1.325 (2) Å, which is considered to have part double-bond character. In the crystalline state, the molecules are linked to two-dimensional hydrogen-bonding networks by intermolecular N—H···O and O—H···N hydrogen bonds. The N···O distance is 2.712 (2) Å, and the O···N distance is 2.666 (2) Å.

Related literature top

For the applications of tetrazoles, see: Chen & Tong (2007); Demko & Sharpless (2001). For related structures, see: Rizk et al. (2005).

Experimental top

A mixture of 3-cyanobenzoic acid (0.147 g, 1.0 mmol), Cd(NO₃)₂.6H₂O (0.345 g, 1 mmol) and water (8 ml) was was heated in a 15-ml Teflon-lined autoclave at 160 ° for 3 days, followed by slow cooling (5 ° h-1) to room temperature. The resulting mixture was washed with water and collected. Then, the obtained solids were put into 20 ml water, and 10% Na₂S aqueous solution was droped to the suspension liquid until that no precipitation appeared. The solution was filtered and the filtrate was acidified with 50% HCl solution until the pH value was 1.0. White products were filtered, washed with water, then dried and collected in 76.2% yield (0.145 g) based on 3-cyanobenzoic acid. Colorless block shaped crystals were collected from the filtrate after the second filtration.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: SHELXTL Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Structure of the title compound with 30% displacement ellipsoids.
	Fig. 2. The two-dimensional hydrogen bonding network of the title compound.
	Fig. 3. Packing of the title compound with view onto the ac plane.

(I) top

Crystal data top

C₈H₆N₄O₂	F(000) = 392
M_r = 190.17	D_x = 1.555 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 785 reflections
a = 5.2501 (10) Å	θ = 2.4–28.0°
b = 16.805 (3) Å	µ = 0.12 mm⁻¹
c = 9.3290 (18) Å	T = 293 K
β = 99.188 (3)°	Block, colorless
V = 812.5 (3) Å³	0.45 × 0.14 × 0.13 mm
Z = 4

Data collection top

Bruker APX CCD diffractometer	1583 independent reflections
Radiation source: fine-focus sealed tube	1425 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scan	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan SADABS (Sheldrick, 2000)	h = −6→6
T_min = 0.949, T_max = 0.985	k = −20→20
5991 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0592P)² + 0.1634P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1583 reflections	Δρ_max = 0.19 e Å⁻³
136 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (3)

Crystal data top

C₈H₆N₄O₂	V = 812.5 (3) Å³
M_r = 190.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.2501 (10) Å	µ = 0.12 mm⁻¹
b = 16.805 (3) Å	T = 293 K
c = 9.3290 (18) Å	0.45 × 0.14 × 0.13 mm
β = 99.188 (3)°

Data collection top

Bruker APX CCD diffractometer	1583 independent reflections
Absorption correction: multi-scan SADABS (Sheldrick, 2000)	1425 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.985	R_int = 0.018
5991 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.19 e Å⁻³
1583 reflections	Δρ_min = −0.24 e Å⁻³
136 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.0644 (2)	0.36005 (6)	0.68049 (12)	0.0471 (3)
O2	0.3759 (2)	0.42002 (6)	0.58687 (13)	0.0496 (3)
H2B	0.410 (4)	0.3707 (14)	0.550 (2)	0.082 (7)*
C1	0.1794 (3)	0.42040 (8)	0.65768 (15)	0.0358 (3)
C2	0.1127 (3)	0.50146 (7)	0.70380 (15)	0.0349 (3)
C3	−0.0705 (3)	0.51184 (8)	0.79498 (16)	0.0403 (4)
H3A	−0.1499	0.4680	0.8296	0.048*
C4	−0.1332 (3)	0.58797 (9)	0.83368 (16)	0.0439 (4)
H4A	−0.2539	0.5950	0.8955	0.053*
C5	−0.0189 (3)	0.65372 (8)	0.78180 (16)	0.0392 (3)
H5A	−0.0640	0.7046	0.8081	0.047*
C6	0.1642 (3)	0.64386 (7)	0.68994 (14)	0.0338 (3)
C7	0.2301 (2)	0.56732 (8)	0.65297 (14)	0.0356 (3)
H7A	0.3544	0.5602	0.5934	0.043*
C8	0.2910 (3)	0.71171 (7)	0.63149 (14)	0.0338 (3)
N1	0.2597 (2)	0.78846 (7)	0.66034 (13)	0.0402 (3)
N2	0.4101 (3)	0.83282 (7)	0.58804 (14)	0.0453 (3)
N3	0.5310 (3)	0.78398 (7)	0.51637 (14)	0.0445 (3)
N4	0.4608 (2)	0.70804 (7)	0.54077 (13)	0.0394 (3)
H1A	0.147 (4)	0.8129 (12)	0.716 (2)	0.067 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0573 (7)	0.0296 (5)	0.0618 (7)	−0.0056 (4)	0.0317 (5)	0.0017 (4)
O2	0.0616 (7)	0.0266 (5)	0.0718 (7)	−0.0021 (4)	0.0446 (6)	−0.0037 (5)
C1	0.0416 (7)	0.0290 (7)	0.0408 (7)	−0.0007 (5)	0.0188 (6)	0.0037 (5)
C2	0.0379 (7)	0.0299 (7)	0.0400 (7)	0.0007 (5)	0.0158 (6)	0.0010 (5)
C3	0.0448 (8)	0.0328 (7)	0.0485 (8)	−0.0023 (6)	0.0231 (6)	0.0013 (6)
C4	0.0468 (8)	0.0408 (8)	0.0510 (8)	0.0015 (6)	0.0285 (7)	−0.0021 (6)
C5	0.0434 (8)	0.0305 (7)	0.0474 (8)	0.0036 (5)	0.0188 (6)	−0.0048 (6)
C6	0.0374 (7)	0.0285 (7)	0.0380 (7)	−0.0004 (5)	0.0133 (5)	−0.0002 (5)
C7	0.0394 (7)	0.0311 (7)	0.0406 (7)	0.0002 (5)	0.0195 (6)	0.0003 (5)
C8	0.0383 (7)	0.0266 (6)	0.0388 (7)	0.0026 (5)	0.0131 (5)	−0.0021 (5)
N1	0.0498 (7)	0.0263 (6)	0.0496 (7)	0.0012 (5)	0.0238 (6)	−0.0017 (5)
N2	0.0564 (8)	0.0290 (6)	0.0559 (8)	−0.0022 (5)	0.0257 (6)	0.0001 (5)
N3	0.0537 (7)	0.0293 (6)	0.0562 (8)	−0.0026 (5)	0.0260 (6)	0.0005 (5)
N4	0.0470 (7)	0.0263 (6)	0.0504 (7)	−0.0010 (5)	0.0247 (5)	−0.0010 (5)

Geometric parameters (Å, º) top

O1—C1	1.2163 (16)	C5—H5A	0.9300
O2—C1	1.3112 (16)	C6—C7	1.3898 (18)
O2—H2B	0.93 (2)	C6—C8	1.4684 (18)
C1—C2	1.4871 (18)	C7—H7A	0.9300
C2—C7	1.3868 (18)	C8—N4	1.3254 (17)
C2—C3	1.3927 (19)	C8—N1	1.3331 (17)
C3—C4	1.3833 (19)	N1—N2	1.3430 (16)
C3—H3A	0.9300	N1—H1A	0.94 (2)
C4—C5	1.381 (2)	N2—N3	1.2882 (17)
C4—H4A	0.9300	N3—N4	1.3576 (16)
C5—C6	1.3961 (18)

C1—O2—H2B	114.1 (14)	C7—C6—C5	119.03 (12)
O1—C1—O2	122.47 (12)	C7—C6—C8	118.74 (11)
O1—C1—C2	124.52 (12)	C5—C6—C8	122.22 (12)
O2—C1—C2	113.01 (11)	C2—C7—C6	120.79 (12)
C7—C2—C3	119.79 (12)	C2—C7—H7A	119.6
C7—C2—C1	119.61 (11)	C6—C7—H7A	119.6
C3—C2—C1	120.59 (11)	N4—C8—N1	106.91 (11)
C4—C3—C2	119.44 (12)	N4—C8—C6	126.31 (11)
C4—C3—H3A	120.3	N1—C8—C6	126.77 (12)
C2—C3—H3A	120.3	C8—N1—N2	109.54 (11)
C5—C4—C3	120.91 (12)	C8—N1—H1A	129.9 (12)
C5—C4—H4A	119.5	N2—N1—H1A	120.5 (12)
C3—C4—H4A	119.5	N3—N2—N1	106.56 (11)
C4—C5—C6	120.02 (12)	N2—N3—N4	110.02 (11)
C4—C5—H5A	120.0	C8—N4—N3	106.96 (10)
C6—C5—H5A	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···N4ⁱ	0.93 (2)	1.76 (2)	2.6664 (15)	164 (2)
N1—H1A···O1ⁱⁱ	0.94 (2)	1.77 (2)	2.7118 (16)	179.1 (19)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₆N₄O₂
M_r	190.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.2501 (10), 16.805 (3), 9.3290 (18)
β (°)	99.188 (3)
V (Å³)	812.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.45 × 0.14 × 0.13

Data collection
Diffractometer	Bruker APX CCD diffractometer
Absorption correction	Multi-scan SADABS (Sheldrick, 2000)
T_min, T_max	0.949, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	5991, 1583, 1425
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.106, 1.07
No. of reflections	1583
No. of parameters	136
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.24

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS (Sheldrick, 2008), SHELXL (Sheldrick, 2008), SHELXTL Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···N4ⁱ	0.93 (2)	1.76 (2)	2.6664 (15)	164 (2)
N1—H1A···O1ⁱⁱ	0.94 (2)	1.77 (2)	2.7118 (16)	179.1 (19)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2.

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

References

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